JP5179818B2 - Metal-containing acidic polishing bath stabilizer - Google Patents
Metal-containing acidic polishing bath stabilizer Download PDFInfo
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- JP5179818B2 JP5179818B2 JP2007242191A JP2007242191A JP5179818B2 JP 5179818 B2 JP5179818 B2 JP 5179818B2 JP 2007242191 A JP2007242191 A JP 2007242191A JP 2007242191 A JP2007242191 A JP 2007242191A JP 5179818 B2 JP5179818 B2 JP 5179818B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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Description
本発明は、金属および過酸化物含有酸性研磨溶液を安定化するための混合物の使用に関する。また、本発明は、尿素と１種以上のアルカンジホスホン酸の混合物を少なくとも１種含む金属および過酸化物含有酸性研磨浴の安定化に適した過酸化物含有溶液を含む。さらに、本発明は、上記混合物を安定剤として含む前記過酸化物含有酸性研磨溶液に関する。最後に本発明は、過酸化物含有酸性溶液を用いて金属表面を化学研磨する方法に関する。 The present invention relates to the use of a mixture for stabilizing metal and peroxide-containing acidic polishing solutions. The present invention also includes a metal containing at least one mixture of urea and one or more alkanediphosphonic acids and a peroxide-containing solution suitable for stabilizing a peroxide-containing acidic polishing bath. Furthermore, this invention relates to the said peroxide containing acidic polishing solution which contains the said mixture as a stabilizer. Finally, the present invention relates to a method for chemically polishing a metal surface using a peroxide-containing acidic solution.
金属表面を化学研磨する方法は、金属表面を平坦化しデバリングするのに用いられる。研磨される金属表面は、酸化性溶液で処理される。この処理は、一般的に酸化性溶液槽への浸漬により行われる。該酸化性溶液は以下の混合水溶液をベースとすることが多い。過酸化物、特に過酸化水素と、無機酸またはその塩、たとえば重フッ化アンモニウム（二フッ化水素アンモニウム、ＮＨ４ＨＦ２）と、その他各種添加剤、たとえば安定剤、光沢剤、抑制剤、界面活性剤および／または粘度調整剤。 The method of chemically polishing a metal surface is used for planarizing and deburring the metal surface. The metal surface to be polished is treated with an oxidizing solution. This treatment is generally performed by immersion in an oxidizing solution tank. The oxidizing solution is often based on the following mixed aqueous solution. Peroxides, in particular hydrogen peroxide, inorganic acids or salts thereof, such as ammonium bifluoride (ammonium difluoride, NH 4 HF 2 ), and various other additives such as stabilizers, brighteners, inhibitors, Surfactant and / or viscosity modifier.
安定剤は過酸化物含有溶液に添加されることが多い。というのは、過酸化水素のような過酸化物は、金属および／または金属イオンの存在下で触媒による分解を受けやすいからである。したがって、金属表面を酸化によりデバリングし平坦化する過酸化物含有研磨浴のように、金属および／または金属イオンと接触する溶液では、特に過酸化物の分解を抑制する安定剤を添加することが重要である。 Stabilizers are often added to peroxide-containing solutions. This is because peroxides such as hydrogen peroxide are susceptible to catalytic decomposition in the presence of metals and / or metal ions. Therefore, in a solution in contact with metal and / or metal ions, such as a peroxide-containing polishing bath that deburring and planarizing the metal surface by oxidation, a stabilizer that suppresses decomposition of the peroxide may be added. is important.
過酸化物に対して用いられる安定剤としては尿素が挙げられる。現状の技術によると、尿素はそれ単独または他の安定剤（たとえば、アンモニウムイオン）と共に過酸化物含有水溶液に添加される。 A stabilizer used for the peroxide includes urea. According to the state of the art, urea is added to the peroxide-containing aqueous solution by itself or together with other stabilizers (eg ammonium ions).
特許文献１は、過酸化物およびその酸性またはアルカリ性溶液に用いる安定剤として、アルキリデン−ジホスホン酸およびその他のホスホン酸反応生成物を使用することを開示している。 Patent Document 1 discloses the use of alkylidene-diphosphonic acid and other phosphonic acid reaction products as stabilizers for peroxides and their acidic or alkaline solutions.
しかし、今日まで用いられている安定剤は、いずれも一定の最大金属イオン濃度以下でしか機能しない。金属イオン濃度がこの上限に達するかそれを超えると、過酸化物含有水溶液は不安定になり、過酸化物が分解されて酸素が発生する。過酸化物含有水溶液において金属イオン濃度がこの臨界点に達すると、原則としてこの過酸化物含有水溶液を使用することはできず、廃棄しなければならない。過酸化物含有水溶液の廃棄をすると、古い溶液の廃棄及び新しい溶液の調製のいずれでもかなりのコストがかかる。 However, all of the stabilizers used to date function only below a certain maximum metal ion concentration. When the metal ion concentration reaches or exceeds this upper limit, the peroxide-containing aqueous solution becomes unstable, and the peroxide is decomposed to generate oxygen. When the metal ion concentration reaches this critical point in a peroxide-containing aqueous solution, in principle, the peroxide-containing aqueous solution cannot be used and must be discarded. Discarding the peroxide-containing aqueous solution can be quite costly, both discarding the old solution and preparing a new solution.
金属イオン含有量の臨界上限は、用いられる金属イオンの種類、過酸化物含有溶液の組成、安定剤によって異なる。たとえば、銅を用いた場合は、臨界上限値は、１０〜３０ｇ／ｌとなり、鉄を用いた場合は、２０〜４０ｇ／ｌとなる。 The critical upper limit of the metal ion content varies depending on the type of metal ion used, the composition of the peroxide-containing solution, and the stabilizer. For example, when copper is used, the critical upper limit is 10 to 30 g / l, and when iron is used, 20 to 40 g / l.
特許文献２は、有機ホスホン酸誘導体と有機ヒドロキシ化合物を含む過酸化水素溶液で安定化の相乗効果が見られることを開示している。この安定剤混合物は、特に湿式精錬、鉱物の分離、洗浄に好適である。 Patent Document 2 discloses that a synergistic effect of stabilization is observed in a hydrogen peroxide solution containing an organic phosphonic acid derivative and an organic hydroxy compound. This stabilizer mixture is particularly suitable for wet refining, mineral separation and washing.
特許文献３は、少なくとも１種のホスホン酸、少なくとも１種の酸化剤、少なくとも1種の短鎖有機カルボン酸を含む洗浄水溶液を開示している。特許文献３で用いてもよい酸化剤として、尿素−過酸化水素が挙げられている。本発明では、通常、尿素をそのまま用い、尿素と過酸化水素との１：１付加物としては用いない。しかし、特許文献３は、過酸化物含有溶液の安定化について記載するものではない。むしろ、特許文献３は磁鉄鉱の除去について記載するものである。ホスホン酸は基本的に、しっかりと付着した磁鉄鉱の固着物を除去するのに用いられる。特許文献３に記載されている洗浄液は、通常８０〜１００℃の温度範囲で用いられる。過酸化物を用いた工程では、過酸化物は通常約６０℃以上で自触媒分解するため、このような高温は用いられない。 Patent Document 3 discloses a cleaning aqueous solution containing at least one phosphonic acid, at least one oxidizing agent, and at least one short-chain organic carboxylic acid. As an oxidizing agent that may be used in Patent Document 3, urea-hydrogen peroxide is cited. In the present invention, urea is usually used as it is and not as a 1: 1 adduct of urea and hydrogen peroxide. However, Patent Document 3 does not describe stabilization of a peroxide-containing solution. Rather, Patent Document 3 describes the removal of magnetite. Phosphonic acid is basically used to remove firmly adhered magnetite deposits. The cleaning liquid described in Patent Document 3 is usually used in a temperature range of 80 to 100 ° C. In a process using a peroxide, such a high temperature is not used because the peroxide usually undergoes autocatalytic decomposition at about 60 ° C. or higher.
特許文献４は、ペルオキシ化合物溶液に用いられる安定剤を開示している。該安定剤は、特定のアミノトリホスホン酸に加えて尿素過化合物を含んでも良い。ペルオキシ化合物溶液は、通常、ｐＨ約７．５〜約１２．５である。ｐＨ７．５未満の溶液は過酸化物漂白液として適さないことが明記されている。それは、ｐＨ値が低いと漂白速度が遅く、効率的な作業ができなくなるからである。 Patent document 4 is disclosing the stabilizer used for a peroxy compound solution. The stabilizer may contain a urea overcompound in addition to the specific aminotriphosphonic acid. The peroxy compound solution typically has a pH of about 7.5 to about 12.5. It is specified that solutions below pH 7.5 are not suitable as peroxide bleaching solutions. This is because if the pH value is low, the bleaching speed is slow and efficient work cannot be performed.
特許文献５は、金属の機械的研磨に適するというペーストまたはスラリーを開示している。該ペーストは、尿素−過酸化物に加えて、特に１−ヒドロキシエタン−１、１ジホスホン酸をキレート剤として含有してもよい。該ペーストまたはスラリーの安定化能については記載されていない。 Patent Document 5 discloses a paste or slurry that is suitable for mechanical polishing of metals. The paste may contain, in addition to urea-peroxide, in particular 1-hydroxyethane-1, 1 diphosphonic acid as a chelating agent. It does not describe the stabilizing ability of the paste or slurry.
従来の安定剤はほかにも欠点を有することが多い。すなわち、従来の安定剤は金属イオン臨界濃度未満でも過酸化物の分解を完全には抑制できず、分解の進行を遅らせるだけである。このため、過酸化物含有溶液の使用中および保管中、たとえば作業中にかなり長い中断をする場合は、過酸化物含有溶液の過酸化物濃度を定期的にチェックする必要があり、触媒による分解で失われた分の過酸化物を補充しなければいけないことも多い。触媒による分解で過酸化物含有溶液の過酸化物濃度が変動すると、工程品質に悪影響が出る。これを避けるためには、定期的に過酸化物含有溶液を分析監視することが必要になり、コストがかかる。 Conventional stabilizers often have other disadvantages. That is, the conventional stabilizer cannot completely suppress the decomposition of the peroxide even when the concentration is lower than the critical metal ion concentration, and only delays the progress of the decomposition. For this reason, it is necessary to periodically check the peroxide concentration of the peroxide-containing solution during use and storage of the peroxide-containing solution, for example during work, and the decomposition by the catalyst. Often, it is necessary to replenish the amount of peroxide lost. If the peroxide concentration of the peroxide-containing solution varies due to decomposition by the catalyst, the process quality is adversely affected. In order to avoid this, it is necessary to periodically analyze and monitor the peroxide-containing solution, which is expensive.
化学的研磨のような過酸化物含有水溶液を用いる多くの処理は、発熱をともなう。そのため、処理中に過酸化物含有水溶液の温度が上昇し、所望の処理温度を維持するためには、過酸化物含有水溶液を冷却する必要がある。また、該温度上昇により、過酸化物が自触媒分解する臨界温度（この自触媒分解も発熱を伴う）以上となる場合がある。過酸化水素水溶液におけるこの臨界温度は約６５℃である。この温度を超えると、安定剤をさらに添加してもこの自触媒分解を抑制することはできない。過酸化物が自触媒分解により分解した場合、市販の安定剤は不可逆的にその効果を失う。従って、その溶液／研磨浴は廃棄しなければならず、新しい溶液の作製が必要になる。 Many processes using peroxide-containing aqueous solutions, such as chemical polishing, are exothermic. For this reason, the temperature of the peroxide-containing aqueous solution rises during the treatment, and it is necessary to cool the peroxide-containing aqueous solution in order to maintain the desired treatment temperature. In addition, the temperature rise may exceed the critical temperature at which the peroxide autocatalytically decomposes (this autocatalytic decomposition also generates heat). This critical temperature in aqueous hydrogen peroxide is about 65 ° C. When this temperature is exceeded, this autocatalytic decomposition cannot be suppressed even if a stabilizer is further added. When the peroxide is decomposed by autocatalytic decomposition, commercially available stabilizers irreversibly lose their effectiveness. Therefore, the solution / polishing bath must be discarded and a new solution must be made.
本発明は、主に、過酸化物含有溶液を安定化するための、尿素および、１つ以上のヒドロキシル基または１つ以上のアミノ基で置換されていてもよい１種以上のアルカンジホスホン酸またはその塩の混合物の使用に関する。 The present invention primarily relates to urea and one or more alkanediphosphonic acids optionally substituted with one or more hydroxyl groups or one or more amino groups for stabilizing peroxide-containing solutions. Or the use of a mixture of its salts.
前記混合物の安定化作用は、該混合物が金属および過酸化物含有酸性研磨溶液の安定化に用いられる場合に特に重要である。 The stabilizing action of the mixture is particularly important when the mixture is used for stabilizing metal and peroxide-containing acidic polishing solutions.
研磨工程の実施中に形成される金属イオンが過酸化物の分解を促進することが知られている。それゆえ、本発明により、特に鉄表面および銅表面に対して、高い金属濃度（たとえば、＞２０ｇ／ｌ）でも研磨浴を使うことができることは驚きであった。 It is known that metal ions formed during the polishing process promote peroxide decomposition. It was therefore surprising that the polishing bath can be used with the present invention even at high metal concentrations (eg> 20 g / l), especially for iron and copper surfaces.
研磨浴は、本発明においては、普通、過酸化物含有酸性水溶液と解される。スラリーやペーストといった機械的研磨を付加するものももちろん考えられるが、それらは本発明の直接の目的ではない。 In the present invention, the polishing bath is usually understood as a peroxide-containing acidic aqueous solution. Of course, those that add mechanical polishing such as slurries and pastes are also contemplated, but they are not the direct object of the present invention.
本発明の他の目的は、以降の明細書および添付の特許請求の範囲から理解される。 Other objects of the invention will be appreciated from the following specification and appended claims.
本発明は、過酸化物含有水溶液用の新規な安定剤に関する。該安定剤は、前記水溶液中に溶解した金属イオン濃度にほぼ左右されずに、確実に過酸化物の分解を抑制する。 The present invention relates to a novel stabilizer for aqueous peroxide-containing solutions. The stabilizer reliably suppresses the decomposition of peroxide without being substantially affected by the concentration of metal ions dissolved in the aqueous solution.
本発明の安定剤は、尿素および、１つ以上のヒドロキシル基または１つ以上のアミノ基で置換されていてもよい１種以上のアルカンジホスホン酸または該アルカンジホスホン酸塩の組合わせを含む。アルカンジホスホン酸は、１個、２個、３個または４個の炭素原子を有する炭化水素鎖を有することが好ましい。前記アルカンジホスホン酸としては、アルキレンジホスホン酸、アミノ置換アルキリデンジホスホン酸、または、ヒドロキシ置換アルキリデンジホスホン酸が挙げられる。特に好適なアルキリデンジホスホン酸としては、１−ヒドロキシエタン−１，１−ジホスホン酸が挙げられる。 The stabilizer of the present invention comprises urea and one or more alkanediphosphonic acids or combinations of the alkanediphosphonates optionally substituted with one or more hydroxyl groups or one or more amino groups. . The alkanediphosphonic acid preferably has a hydrocarbon chain having 1, 2, 3 or 4 carbon atoms. Examples of the alkanediphosphonic acid include alkylene diphosphonic acid, amino-substituted alkylidene diphosphonic acid, and hydroxy-substituted alkylidene diphosphonic acid. Particularly suitable alkylidene diphosphonic acids include 1-hydroxyethane-1,1-diphosphonic acid.
本発明に係る上記新規安定剤は、尿素の重量比が遊離のアルカンジホスホン酸に対して１００：１〜２０：１の範囲にある場合に、特に高い効果を発揮する。好ましくは該重量比は６０：１〜３５：１であり、特に５０：１程度が好ましい。 The novel stabilizer according to the present invention exhibits a particularly high effect when the weight ratio of urea is in the range of 100: 1 to 20: 1 with respect to free alkanediphosphonic acid. The weight ratio is preferably 60: 1 to 35: 1, and particularly preferably about 50: 1.
前記安定剤は、過酸化物含有水溶液を安定化させる作用を持つ。これは主に、過酸化水素含有水溶液に関係するが、それ以外の過酸化物含有溶液も同様に安定化することができる。たとえば、過硫酸および／または過酢酸のようなペルオキシカルボン酸、またはその塩を含む溶液を安定化することができる。 The stabilizer has an effect of stabilizing the peroxide-containing aqueous solution. This mainly relates to hydrogen peroxide-containing aqueous solutions, but other peroxide-containing solutions can be stabilized as well. For example, a solution containing a peroxycarboxylic acid such as persulfuric acid and / or peracetic acid, or a salt thereof can be stabilized.
安定化された過酸化水素水溶液の濃度は、約３０％または約３５％とすることができる。また、該濃度はそれより低いものであってもよく、たとえば、２０％以下、１０％以下、または５％以下であってもよい。 The concentration of the stabilized aqueous hydrogen peroxide solution can be about 30% or about 35%. Further, the concentration may be lower, for example, 20% or less, 10% or less, or 5% or less.
本発明の別の態様として、本発明の安定剤を用いて安定化された溶液が挙げられる。この溶液は、安定剤、１種以上の過酸化物、水以外の成分を含んでもよい。過酸化物含有溶液は該構成成分以外の１種以上の酸を含むことが多い。このような酸としては、例えば、塩酸、硫酸、リン酸、過塩素酸、フッ化水素酸のような鉱酸および／またはカルボン酸やスルホン酸のような有機酸が挙げられる。 Another embodiment of the present invention includes a solution stabilized with the stabilizer of the present invention. This solution may contain components other than the stabilizer, one or more peroxides, and water. The peroxide-containing solution often contains one or more acids other than the constituent components. Examples of such an acid include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, and hydrofluoric acid, and / or organic acids such as carboxylic acid and sulfonic acid.
本発明の安定剤は、過酸化物含有水溶液に純物質または溶液として加えることができる。一般的に、過酸化物含有水溶液における安定剤の濃度は、０．１〜３．０ｗｔ．％であり、好ましくは０．２〜３．０ｗｔ．％、特に０．４〜１．０ｗｔ．％程度が好ましい。 The stabilizer of the present invention can be added to the peroxide-containing aqueous solution as a pure substance or as a solution. Generally, the concentration of the stabilizer in the peroxide-containing aqueous solution is 0.1 to 3.0 wt. %, Preferably 0.2 to 3.0 wt. %, Especially 0.4 to 1.0 wt. % Is preferred.
尿素とアルキリデンジホスホン酸という、本発明の安定剤に含まれる物質は、個々には安定剤として既知であり、個々に安定剤として使用されている。しかし、尿素、アルキリデンジホスホン酸単独では、上述したような従来の安定剤の欠点が現れてしまう。 The substances contained in the stabilizers according to the invention, urea and alkylidene diphosphonic acids, are known individually as stabilizers and are used individually as stabilizers. However, urea and alkylidene diphosphonic acid alone have the disadvantages of the conventional stabilizers described above.
しかし驚くべきことに、尿素と１種以上のアルカンジホスホン酸を組合わせることで、新規な特性を発揮する過酸化物含有水溶液用の安定剤が得られることがわかった。すなわち、尿素および１種以上のアルカンジホスホン酸またはアルカンジホスホン酸の塩を含む安定剤は、下記の特性を有する。該特性は、たとえば安定化された過酸化物含有水溶液が金属表面処理用の化学研磨浴として用いられる場合などの様々な用途において重要である。化学研磨浴という語は、浸漬浴だけでなく、安定化された過酸化物含有溶液の過酸化物の化学反応に基づく金属表面の研磨またはデバリングを目的としたあらゆる形態の利用を含むものである。 Surprisingly, however, it has been found that a combination of urea and one or more alkanediphosphonic acids can provide a stabilizer for peroxide-containing aqueous solutions that exhibits novel properties. That is, a stabilizer comprising urea and one or more alkanediphosphonic acids or salts of alkanediphosphonic acids has the following properties. This property is important in a variety of applications, such as when a stabilized peroxide-containing aqueous solution is used as a chemical polishing bath for metal surface treatment. The term chemical polishing bath includes all forms of use for polishing or deburring metal surfaces based not only on immersion baths but also on chemical reactions of peroxides in stabilized peroxide-containing solutions.
１． 本発明の安定剤を用いれば、過酸化物含有水溶液、たとえば化学研磨浴は、金属イオンが飽和状態になるまで、または任意で添加される１種以上の無機酸のような反応性物質を消耗するまで、過酸化物含有水溶液の作用、特にその酸化作用がひどく劣化することなく用いることができる。さらに、反応性物質を消耗した溶液は、該反応性物質を補充するだけでその機能を完全に回復するので、溶液を廃棄する必要が無い。 1. With the stabilizers of the present invention, peroxide-containing aqueous solutions, such as chemical polishing baths, deplete reactive materials such as one or more inorganic acids that are added until metal ions are saturated or optionally added. Until that time, the action of the peroxide-containing aqueous solution, particularly the oxidation action thereof, can be used without severely deteriorating. In addition, the solution depleted of the reactive substance completely recovers its function only by replenishing the reactive substance, so there is no need to discard the solution.
２． 過酸化物含有水溶液が過熱状態になり、過酸化物の自触媒分解が起こったとしても、本発明の安定剤は通常ダメージを受けない。過酸化物含有水溶液が完全に反応し、臨界温度未満に冷却された後、過酸化物を補充すれば、過酸化物含有水溶液は限定なしに再度使用することができ、安定剤の安定化作用は劣化しない。 2. Even if the peroxide-containing aqueous solution becomes overheated and the autocatalytic decomposition of the peroxide occurs, the stabilizer of the present invention is not usually damaged. After the peroxide-containing aqueous solution is completely reacted and cooled to below the critical temperature, if the peroxide is replenished, the peroxide-containing aqueous solution can be used again without limitation, and the stabilizing effect of the stabilizer. Does not deteriorate.
３． 本発明の安定剤は、従来技術の個々の化合物やその他の安定剤より飛躍的に優れた安定化作用を示すことが多い。すなわち、本発明の安定剤を含む過酸化物含有水溶液は、ワークのデバリングまたは研磨における化学研磨浴といった使用中、および、作業中断時のような保存中においても、過酸化物の分解によりわずかな量の酸素しか失わないことがわかった。したがって、無機酸のような反応性物質を含んでもよい過酸化物含有水溶液を経済的に最大限使用することができる。 3. The stabilizers of the present invention often exhibit a stabilizing action that is significantly superior to individual compounds and other stabilizers of the prior art. That is, the peroxide-containing aqueous solution containing the stabilizer of the present invention is slightly decomposed by peroxide decomposition during use such as a chemical polishing bath in workpiece deburring or polishing, and during storage such as operation interruption. It was found that only an amount of oxygen was lost. Therefore, a peroxide-containing aqueous solution that may contain a reactive substance such as an inorganic acid can be economically used to the maximum extent.
４． 本発明に係る安定剤が優れた安定化作用を示すため、アンモニウムイオンのような高価な有機添加剤を使用する必要がなくなった。これによって、廃液と濃縮液の処理に伴う費用が大幅に低減される。使用済の過酸化物含有水溶液は、簡単な中和処理および沈殿による金属イオンの分離処理等により処理される。したがって、アンモニウムイオン成分の使用に伴う錯体の特殊処理または研磨浴やスラッジの焼却は不要となった。 4). Since the stabilizer according to the present invention exhibits an excellent stabilizing action, it is no longer necessary to use expensive organic additives such as ammonium ions. This greatly reduces the costs associated with processing the waste and concentrate. The spent peroxide-containing aqueous solution is treated by a simple neutralization treatment, a separation treatment of metal ions by precipitation, or the like. Therefore, special treatment of the complex accompanying use of the ammonium ion component or incineration of the polishing bath and sludge is no longer necessary.
５． 上記過酸化物含有水溶液が金属表面処理用の化学研磨浴として用いられる場合、該研磨浴の組成は、反応性物質である酸、過酸化物および安定剤に限定することができる。これら以外の物質の添加も可能であるが、通常はその必要はなく、さらに大幅なコストダウンが可能になる。 5. When the peroxide-containing aqueous solution is used as a chemical polishing bath for metal surface treatment, the composition of the polishing bath can be limited to acids, peroxides and stabilizers which are reactive substances. Addition of substances other than these is possible, but usually it is not necessary, and the cost can be greatly reduced.
６． 上記過酸化物含有水溶液が化学研磨浴として用いられる場合、従来技術の方法に相関して研磨速度と研磨浴の効率は上昇するが、品質の低下はない。 6). When the peroxide-containing aqueous solution is used as a chemical polishing bath, the polishing rate and the efficiency of the polishing bath are increased in correlation with the conventional method, but the quality is not deteriorated.
上記有利な特性を有する点で本発明の安定剤は、従来の安定剤とは異なるものである。該特性は、安定剤の構成成分同士の予期されなかった相乗効果により得られたものである。該相乗効果は、構成成分である尿素とアルカンジホスホン酸が重量比１００：１〜２０：１で用いられた時、特に顕著になる。 The stabilizer of the present invention is different from conventional stabilizers in that it has the above advantageous characteristics. This property is obtained due to an unexpected synergistic effect between the components of the stabilizer. The synergistic effect is particularly noticeable when the constituent components urea and alkanediphosphonic acid are used in a weight ratio of 100: 1 to 20: 1.
本発明の他の態様は、金属表面を本発明の安定剤を含む過酸化物含有研磨浴を用いて化学研磨する方法に関する。化学研磨とは、酸化性酸性溶液を用いて金属表面を平坦化しデバリングすることを意味する。本発明の方法を用いて、種々の金属を含むワークの表面を化学研磨することができる。該方法は、たとえば、銅や銅合金のワーク等の銅含有金属表面の研磨に適用することができる。また、該方法は、たとえば、炭素鋼および軟鉄から製造された構造の鉄含有金属表面の研磨に適用することもできる。 Another aspect of the present invention relates to a method of chemically polishing a metal surface using a peroxide-containing polishing bath containing the stabilizer of the present invention. Chemical polishing means flattening and deburring a metal surface using an oxidizing acidic solution. Using the method of the present invention, the surface of a workpiece containing various metals can be chemically polished. The method can be applied, for example, to polishing a copper-containing metal surface such as a copper or copper alloy workpiece. The method can also be applied to polishing of an iron-containing metal surface having a structure manufactured from carbon steel and soft iron, for example.
炭素鋼を化学研磨するにあたって、従来技術においては酸化剤に加えて重フッ化アンモニウムを含有する溶液が用いられる。本発明に係る方法を用いる場合は、重フッ化アンモニウムを同濃度のフッ化水素酸と交換すればよい。これにより、研磨浴で使用される構成成分のコストが低減されるだけでなく、アンモニア含有浴およびスラッジの廃棄に伴うコストも低減される。さらに、このようなフッ化水素酸含有研磨浴を用いれば、金属ワークの処理速度が飛躍的に速くなる。すなわち、従来の研磨浴を用いた場合の何倍もの速度になる。また、本発明においては、従来の研磨浴で必要であった多くの有機添加物も不要になる。 In chemically polishing carbon steel, in the prior art, a solution containing ammonium bifluoride in addition to an oxidizing agent is used. When the method according to the present invention is used, ammonium bifluoride may be exchanged with the same concentration of hydrofluoric acid. This not only reduces the cost of the components used in the polishing bath, but also reduces the costs associated with discarding the ammonia-containing bath and sludge. Furthermore, when such a hydrofluoric acid-containing polishing bath is used, the processing speed of the metal workpiece is remarkably increased. That is, the speed is many times higher than when a conventional polishing bath is used. Further, in the present invention, many organic additives necessary for the conventional polishing bath are also unnecessary.
本発明の化学研磨方法は、少なくとも、安定化された過酸化物含有水溶液を適切な手法で金属表面に接触させることを特徴とする。この工程は、たとえば、ワークを研磨浴に浸漬することで行うこともできるし、また、研磨される内部空間に過酸化物含有水溶液を通過させたり、ワークの表面にスプレーするといった他の方法で行うこともできる。１以上のワークを研磨するのに、過酸化物含有水溶液に浸漬させる場合、研磨浴の攪拌を行うことが有効である場合が多い。これによって、作業時間が短縮され、金属表面が均一に研磨される。安定化された過酸化物含有水溶液は、必要に応じて、光沢剤、抑制剤、界面活性剤、および／または粘度調整剤のような添加剤を含んでいてもよい。 The chemical polishing method of the present invention is characterized in that at least a stabilized peroxide-containing aqueous solution is brought into contact with a metal surface by an appropriate technique. This step can be performed, for example, by immersing the workpiece in a polishing bath, or by passing the peroxide-containing aqueous solution through the internal space to be polished or by spraying the surface of the workpiece. It can also be done. When polishing one or more workpieces, it is often effective to stir the polishing bath when immersed in a peroxide-containing aqueous solution. Thereby, the working time is shortened and the metal surface is uniformly polished. The stabilized peroxide-containing aqueous solution may contain additives such as brighteners, inhibitors, surfactants, and / or viscosity modifiers as necessary.
研磨は、通常、室温またはそれよりわずかに高い温度、たとえば２０〜４５℃で行われる。最適な研磨時間は、温度、研磨溶液の組成、研磨対象の金属表面の組成、初期粗さ等の多くの要因に左右される。しかし、本発明の安定剤を用いることで、研磨溶液中の金属イオン濃度にはほとんど左右されなくなる。 Polishing is usually performed at room temperature or slightly above, for example, 20-45 ° C. The optimum polishing time depends on many factors such as temperature, polishing solution composition, composition of the metal surface to be polished, and initial roughness. However, the use of the stabilizer of the present invention hardly depends on the metal ion concentration in the polishing solution.
ワークを研磨浴中で処理、またはワークに過酸化物含有水溶液を接触させた後、該ワークを通常脱イオン水でリンスして乾燥する。 After the workpiece is treated in a polishing bath or brought into contact with a peroxide-containing aqueous solution, the workpiece is usually rinsed with deionized water and dried.
以下の実施例を示して、本発明をより詳細に説明する。 The following examples illustrate the invention in more detail.
（実施例１、比較例１）
炭素鋼Ｃ４５処理用の化学研磨浴
(Example 1, Comparative Example 1)
Chemical polishing bath for carbon steel C45 treatment
Ａ―従来技術に係る研磨浴：
組成（ｗｔ．％）：
二フッ化水素アンモニウム ０．８％
尿素 １．８％
シュウ酸 ０．５％
過酸化水素（３５％） １０．０％
水 残部
パラメーター：
温度 ３０℃
鉄研磨速度（活性）： ５０ｍｇ／（ｄｍ２ｍｉｎ）
A—Polishing bath according to the prior art:
Composition (wt.%):
Ammonium hydrogen difluoride 0.8%
Urea 1.8%
Oxalic acid 0.5%
Hydrogen peroxide (35%) 10.0%
Water balance
parameter:
Temperature 30 ° C
Iron polishing rate (activity): 50 mg / (dm 2 min)
結果：
研磨表面は光沢があり、端部はデバリングされていた。
溶解した鉄の濃度が２０ｇ／ｌまでの処理で、該濃度が高くなると過酸化水素の消耗が急速に激しくなった。該濃度が３０ｇ／ｌを超えると、研磨浴は使用できなくなり、一部を入れ替えて再生せざるを得なくなった。研磨溶液中の鉄濃度が２５ｇ／ｌ以上では難溶性の沈殿（塩被覆）が増加した。
result:
The polished surface was glossy and the edges were deburred.
In the treatment with the dissolved iron concentration up to 20 g / l, the consumption of hydrogen peroxide increased rapidly as the concentration increased. When the concentration exceeded 30 g / l, the polishing bath could not be used, and a part of the polishing bath had to be replaced and regenerated. When the iron concentration in the polishing solution was 25 g / l or more, the hardly soluble precipitate (salt coating) increased.
二フッ化水素アンモニウムの濃度を上げることで、８０ｍｇ／（ｄｍ２ｍｉｎ）まで活性を上げることが可能であった。高活性にすると、研磨表面は光沢が無くなり、粗くなった。 It was possible to increase the activity to 80 mg / (dm 2 min) by increasing the concentration of ammonium hydrogen fluoride. With high activity, the polished surface was not glossy and roughened.
Ｂ―本発明に係る研磨浴：
組成（ｗｔ．％）：
フッ化水素酸 ０．７％
尿素 ０．７％
１−ヒドロキシエタン−１、１−ジホスホン酸 ０．０２％
過酸化水素（３５％） ２０．０％
水 残部
パラメーター：
温度： ３０℃
活性： ２００ｍｇ／（ｄｍ２ｍｉｎ）
B—Polishing bath according to the invention:
Composition (wt.%):
Hydrofluoric acid 0.7%
Urea 0.7%
1-hydroxyethane-1,1-diphosphonic acid 0.02%
Hydrogen peroxide (35%) 20.0%
Water balance
parameter:
Temperature: 30 ° C
Activity: 200 mg / (dm 2 min)
結果：
研磨表面は平坦で光沢があり、端部はデバリングされていた。
フッ化水素酸および安定剤の濃度を上げることで、研磨品質を損なうことなく活性を６００ｍｇ／（ｄｍ２ｍｉｎ）まで上げることができた。しかも、研磨浴中の沈殿は観察されなかった。また、過酸化水素の消耗は増加しなかった。研磨浴は鉄濃度が６０ｇ／ｌになるまで使用できた。
result:
The polished surface was flat and glossy, and the edges were deburred.
By increasing the concentration of hydrofluoric acid and stabilizer, the activity could be increased to 600 mg / (dm 2 min) without impairing the polishing quality. Moreover, no precipitation in the polishing bath was observed. Also, the consumption of hydrogen peroxide did not increase. The polishing bath could be used until the iron concentration reached 60 g / l.
研磨浴（Ｂ）は研磨浴（Ａ）と比較して、活性が最大で８倍高くなり、そのため作業時間が短く、しかも耐用期間が３倍以上であった。その上、研磨浴（Ｂ）は研磨浴（Ａ）と比較して化合物にかかるコストがずっと安かった。 The activity of the polishing bath (B) was up to 8 times higher than that of the polishing bath (A), so that the working time was short and the service life was more than 3 times. Moreover, the polishing bath (B) was much cheaper for the compound compared to the polishing bath (A).
（実施例２、比較例２）
銅処理用の化学研浴
(Example 2, comparative example 2)
Chemical bath for copper treatment
Ａ―従来技術に係る研磨浴
組成（ｗｔ．％）：
硫酸（９６％） １．０％
過酸化水素（３５％） １４．０％
安定剤（市販） １．０％
水 残部
パラメーター：
温度：３５℃
研磨速度： ０．１ｇ／（ｄｍ２ｍｉｎ）
A-Polishing bath according to the prior art
Composition (wt.%):
Sulfuric acid (96%) 1.0%
Hydrogen peroxide (35%) 14.0%
Stabilizer (commercially available) 1.0%
Water balance
parameter:
Temperature: 35 ° C
Polishing rate: 0.1 g / (dm 2 min)
結果：
研磨表面は光沢が良く、端部はデバリングされていた。
銅の含有濃度が１０ｇ／ｌ以上になると、過酸化水素の消耗が増加した。該濃度が２０ｇ／ｌを超えると、研磨表面の品質が極端に劣化し、過酸化水素の消耗が急激に激しくなった。
result:
The polished surface was glossy and the edges were deburred.
When the copper concentration was 10 g / l or more, the consumption of hydrogen peroxide increased. When the concentration exceeded 20 g / l, the quality of the polished surface was extremely deteriorated, and the consumption of hydrogen peroxide increased rapidly.
Ｂ―本発明に係る研磨浴
組成（ｗｔ．％）：
硫酸（９６％） １．０％
過酸化水素（３５％） １４．０％
尿素 ０．４％
１−ヒドロキシエタン−１、１−ジホスホン酸 ０．０１％
水 残部
パラメーター：
温度：３５℃
研磨速度：０．１ｇ／（ｄｍ２ｍｉｎ）
B—Polishing bath according to the invention
Composition (wt.%):
Sulfuric acid (96%) 1.0%
Hydrogen peroxide (35%) 14.0%
Urea 0.4%
1-hydroxyethane-1,1-diphosphonic acid 0.01%
Water balance
parameter:
Temperature: 35 ° C
Polishing rate: 0.1 g / (dm 2 min)
結果
銅の含有濃度が５０ｇ／ｌ以下では、光沢表面が得られた。銅の含有濃度が３０ｇ／ｌ以下では、過酸化水素の消耗は変化しなかった。濃度が３０ｇ／ｌを超えると、作業１時間あたりでは過酸化水素の消耗にわずかな増加がみられた。これは、本発明に係る研磨浴の耐用期間が従来に比べて２．５〜３倍であることと一致する。
Results A glossy surface was obtained when the copper concentration was 50 g / l or less. When the copper concentration was 30 g / l or less, the consumption of hydrogen peroxide did not change. When the concentration exceeded 30 g / l, there was a slight increase in the consumption of hydrogen peroxide per hour of work. This coincides with the fact that the service life of the polishing bath according to the present invention is 2.5 to 3 times that of the prior art.
Claims (16)
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| WO2011068830A2 (en) | 2009-12-01 | 2011-06-09 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Porous geopolymer materials |
| US9365691B2 (en) | 2010-08-06 | 2016-06-14 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using intrepenetrating inorganic-organic composite gels |
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| CN108505042A (en) * | 2018-05-23 | 2018-09-07 | 深圳市百诣良科技发展有限公司 | A kind of the PCB thinned copper liquid of high speed and preparation method |
| CN112831789A (en) * | 2020-12-31 | 2021-05-25 | 中山市和胜智能家居配件有限公司 | Chemical polishing additive and preparation method and application thereof |
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| NL130828C (en) | 1959-06-03 | |||
| US3234140A (en) | 1964-06-05 | 1966-02-08 | Monsanto Co | Stabilization of peroxy solutions |
| US3740187A (en) * | 1971-06-03 | 1973-06-19 | Monsanto Co | Processes for bleaching textiles |
| JPS526691B2 (en) * | 1971-10-19 | 1977-02-24 | ||
| US4059678A (en) * | 1973-02-02 | 1977-11-22 | Fmc Corporation | Stabilization of iron-containing acidic hydrogen peroxide solutions |
| BE818616A (en) | 1973-08-30 | 1975-02-10 | STABILIZED AQUEOUS SOLUTIONS OF HYDROGEN PEROXIDE | |
| DD212493A1 (en) * | 1982-12-14 | 1984-08-15 | Wolfgang Thiele | PROCESS FOR PREPARING A STORAGE STABLE CARBAMIDE PERHYDRATE |
| JP3445285B2 (en) * | 1991-07-09 | 2003-09-08 | トモエ化学工業株式会社 | Stable liquid concentrate containing active oxygen, fertilizer application / sterilization method using the composition, and treating agent |
| US5273733A (en) * | 1992-04-14 | 1993-12-28 | Eka Nobel Inc. | Process for the production of chlorine dioxide |
| DE4232612A1 (en) * | 1992-09-29 | 1994-03-31 | Henkel Kgaa | Removal of magnetite deposits in water-bearing systems |
| JPH11350170A (en) * | 1998-06-03 | 1999-12-21 | Nippon Peroxide Co Ltd | Chemical dissolution treating solution for iron or ferroalloy |
| US6217416B1 (en) * | 1998-06-26 | 2001-04-17 | Cabot Microelectronics Corporation | Chemical mechanical polishing slurry useful for copper/tantalum substrates |
| US6830503B1 (en) * | 2002-01-11 | 2004-12-14 | Cabot Microelectronics Corporation | Catalyst/oxidizer-based CMP system for organic polymer films |
| US6755721B2 (en) * | 2002-02-22 | 2004-06-29 | Saint-Gobain Ceramics And Plastics, Inc. | Chemical mechanical polishing of nickel phosphorous alloys |
| US6604987B1 (en) * | 2002-06-06 | 2003-08-12 | Cabot Microelectronics Corporation | CMP compositions containing silver salts |
| US6803354B2 (en) * | 2002-08-05 | 2004-10-12 | Henkel Kormanditgesellschaft Auf Aktien | Stabilization of hydrogen peroxide in acidic baths for cleaning metals |
| CN1333444C (en) | 2002-11-12 | 2007-08-22 | 阿科玛股份有限公司 | Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents |
| JP4226389B2 (en) * | 2003-04-09 | 2009-02-18 | 長庚大學 | Metal surface treatment method using metal surface treatment aqueous solution |
| US7390744B2 (en) * | 2004-01-29 | 2008-06-24 | Applied Materials, Inc. | Method and composition for polishing a substrate |
| JP2005220365A (en) * | 2004-02-03 | 2005-08-18 | Mitsubishi Gas Chem Co Inc | Chemical polishing solution for copper and copper alloy |
| CN101163776A (en) * | 2004-11-19 | 2008-04-16 | 霍尼韦尔国际公司 | Selective removal chemistries for semiconductor applications, methods of production and uses thereof |
| EP1793016A1 (en) * | 2005-12-01 | 2007-06-06 | Elpochem AG | Polishing and deburring composition for workpieces of carbon steel and method of chemical polishing and deburring |
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2007
- 2007-09-17 SI SI200731632T patent/SI1903081T1/en unknown
- 2007-09-17 PT PT70182209T patent/PT1903081E/en unknown
- 2007-09-17 EP EP07018220.9A patent/EP1903081B1/en active Active
- 2007-09-17 PL PL07018220T patent/PL1903081T3/en unknown
- 2007-09-17 DK DK07018220.9T patent/DK1903081T3/en active
- 2007-09-17 ES ES07018220.9T patent/ES2533349T3/en active Active
- 2007-09-19 US US11/857,564 patent/US20080067149A1/en not_active Abandoned
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| PT1903081E (en) | 2015-04-07 |
| EP1903081A3 (en) | 2010-09-29 |
| EP1903081B1 (en) | 2015-01-28 |
| JP2008101272A (en) | 2008-05-01 |
| SI1903081T1 (en) | 2015-06-30 |
| CA2602992A1 (en) | 2008-03-19 |
| DK1903081T3 (en) | 2015-03-23 |
| US20080067149A1 (en) | 2008-03-20 |
| ES2533349T3 (en) | 2015-04-09 |
| PL1903081T3 (en) | 2015-05-29 |
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